FR2900148A1 - CERAMICS BASED ON LANTHAN DOPED BARIUM TITANATE, NOVEL PREPARATION METHOD AND USES. - Google Patents
CERAMICS BASED ON LANTHAN DOPED BARIUM TITANATE, NOVEL PREPARATION METHOD AND USES. Download PDFInfo
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- FR2900148A1 FR2900148A1 FR0603414A FR0603414A FR2900148A1 FR 2900148 A1 FR2900148 A1 FR 2900148A1 FR 0603414 A FR0603414 A FR 0603414A FR 0603414 A FR0603414 A FR 0603414A FR 2900148 A1 FR2900148 A1 FR 2900148A1
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- Prior art keywords
- barium titanate
- lanthanum
- temperature
- ceramics
- doped barium
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- 239000000919 ceramic Substances 0.000 title claims abstract description 38
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 33
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000003990 capacitor Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052746 lanthanum Inorganic materials 0.000 claims description 15
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910010062 TiCl3 Inorganic materials 0.000 claims 1
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 claims 1
- 238000005259 measurement Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009770 conventional sintering Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 2
- 238000002490 spark plasma sintering Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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Abstract
La présente invention concerne un nouveau procédé de préparation de céramiques à base de titanate de baryum dopé au lanthane comprenant les étapes :(a) frittage flash de poudres de titanate de baryum dopé au lanthane,(b) traitement thermique du matériau ainsi obtenu, sous atmosphère d'air, ou sous atmosphère oxydante.L'invention concerne aussi des céramiques à base de titanate de baryum dopé au lanthane, possédant une partie réelle de la permittivité diélectrique relative très élevée, ainsi que leur utilisation pour l'obtention de condensateurs à forte capacité et de capacité volumique élevée pour des tenues en tension importantes.The present invention relates to a novel process for the preparation of lanthanum-doped barium titanate ceramics comprising the steps of: (a) flash sintering of lanthanum-doped barium titanate powders, (b) heat treatment of the material thus obtained, The invention also relates to ceramics based on lanthanum-doped barium titanate, having a real part of the very high relative dielectric permittivity, as well as their use for obtaining capacitors with high capacity and high volume capacity for high voltage holdings.
Description
La présente invention concerne un nouveau procédé de préparation deThe present invention relates to a novel process for the preparation of
céramiques à base de titanate de baryum dopé au lanthane, les céramiques ainsi obtenues, et leurs utilisations. ceramics based on lanthanum-doped barium titanate, the ceramics thus obtained, and their uses.
Les appareillages électroniques intègrent de plus en plus de fonctionnalités dans des volumes de plus en plus restreints. La taille des composants doit donc sans cesse être réduite, et dans le même temps, leurs propriétés doivent être conservées, voire augmentées. C'est en particulier le cas des condensateurs pour lesquels on souhaite pouvoir disposer d'une capacité volumique élevée tout en maintenant une rigidité diélectrique importante. Electronic devices are integrating more and more features into smaller and smaller volumes. The size of the components must therefore be constantly reduced, and at the same time, their properties must be preserved or even increased. This is particularly the case of capacitors for which it is desired to have a high volume capacity while maintaining a high dielectric strength.
Le titanate de baryum (BaTiO3) possède des propriétés ferroélectriques élevées et ses domaines d'applications sont multiples. Il présente par exemple un grand intérêt pour la fabrication de condensateurs multicouches, de dispositifs électrooptiques ou de mémoires DRAM (Dynamic Random Acces Memories). Les températures et les tensions auxquelles sont exposées ces matériaux sont sans cesse plus grandes. Il existe donc un réel besoin d'obtention de matériaux à base de titanate de baryum de plus en plus performants, afin de réaliser des condensateurs présentant des capacités et des densités d'énergies élevées. Barium titanate (BaTiO3) has high ferroelectric properties and has many applications. It presents for example a great interest for the manufacture of multilayer capacitors, electro-optical devices or DRAM (Dynamic Random Acces Memories) memories. The temperatures and voltages at which these materials are exposed are constantly increasing. There is therefore a real need for obtaining increasingly high-performance barium titanate materials in order to produce capacitors with high energy capacities and densities.
De nombreux travaux ont été menés dans ce sens, en particulier afin d'identifier les facteurs importants qui influencent les propriétés ferroélectriques des céramiques à base de BaTiO3. Ainsi on a mis en évidence que les performances de ces céramiques peuvent être améliorées en contrôlant certains paramètres comme la taille des grains ou l'homogénéité de BaTiO3. L'utilisation de BaTiO3 nanométrique permet d'accroître considérablement la partie réelle de la permittivité diélectrique relative des céramiques obtenues en comparaison avec les matériaux préparés à partir de BaTiO3 de taille micrométrique (US-6,905,649). Le procédé de préparation influence également les paramètres des matériaux obtenus. Plusieurs études ont ainsi mis en évidence l'intérêt de la technique de frittage flash par rapport au frittage classique (J. Mat. Sei., 36, 2001, 2329-2334), qui permet d'éviter la croissance exagérée des grains rencontrée lors du chauffage par des techniques conventionnelles. Numerous studies have been conducted in this direction, in particular to identify the important factors that influence the ferroelectric properties of BaTiO3-based ceramics. Thus, it has been demonstrated that the performance of these ceramics can be improved by controlling certain parameters such as the grain size or the homogeneity of BaTiO3. The use of nanoscale BaTiO3 makes it possible to considerably increase the real part of the relative dielectric permittivity of the ceramics obtained in comparison with the materials prepared from micron-sized BaTiO3 (US-6,905,649). The preparation process also influences the parameters of the materials obtained. Several studies have thus highlighted the interest of the technique of flash sintering compared to conventional sintering (J. Matt Sci., 36, 2001, 2329-2334), which makes it possible to avoid the excessive growth of the grains encountered during heating by conventional techniques.
La technique de frittage flash est une technique de mise en forme des matériaux, similaire au pressage conventionnel à chaud. Lors de la mise en oeuvre de cette technique, les précurseurs sont introduits dans une matrice, par exemple du graphite, qui permet d'appliquer une pression uni-axiale lors du frittage. Un courant électrique continu, continu-pulsé, ou alternatif est appliqué par l'intermédiaire d'électrodes, traverse la matrice de pressage conductrice et peut même, dans les cas appropriés traverser l'échantillon. La matrice agit ainsi en tant que source de chauffage, ce qui permet d'obtenir des vitesses de montée en température élevées, et de s'affranchir de l'utilisation d'un four traditionnel. Les objets ainsi frittés sont obtenus à des températures plus faibles et les temps de frittage sont significativement plus courts que lors de procédures de frittage conventionnelles. Ils présentent de plus une très grande compacité et la croissance des grains au cours du frittage est fortement inhibée. The flash sintering technique is a material shaping technique, similar to conventional hot pressing. During the implementation of this technique, the precursors are introduced into a matrix, for example graphite, which makes it possible to apply a uni-axial pressure during sintering. Continuous, pulsed, or alternating electric current is applied via electrodes, passes through the conductive pressing die, and may even pass through the sample in appropriate cases. The matrix thus acts as a heating source, which makes it possible to obtain high temperature rise rates, and to overcome the use of a conventional oven. The thus sintered objects are obtained at lower temperatures and the sintering times are significantly shorter than in conventional sintering procedures. They also have a very high compactness and grain growth during sintering is strongly inhibited.
Un autre moyen pour améliorer les propriétés des céramiques consiste à introduire un élément dopant dans le matériau utilisé. Dans le cas de BaTiO3, le lanthane a montré une influence considérable sur les propriétés électriques et conductrices des céramiques obtenues (J. Am. Ceram. Soc., 84, 3, 2001, 531-538), notamment en augmentant la valeur de la partie réelle de la permittivité diélectrique relative et en diminuant la température de Curie. Les permittivités ainsi mesurées à 1 kHz, et à la température de Curie, sont de l'ordre de 10 000. Another way to improve the properties of ceramics is to introduce a doping element into the material used. In the case of BaTiO 3, lanthanum has shown a considerable influence on the electrical and conductive properties of the ceramics obtained (J. Am Ceram Soc., 84, 3, 2001, 531-538), in particular by increasing the value of the real part of the relative dielectric permittivity and decreasing the Curie temperature. The permittivities thus measured at 1 kHz, and at the Curie temperature, are of the order of 10 000.
Dans le but de continuer à augmenter la partie réelle de la permittivité diélectrique relative des céramiques, la Demanderesse a mis en évidence que de façon 30 surprenante, en choisissant de façon appropriée les conditions opératoires de leur procédé de fabrication, les performances diélectriques des matériaux obtenus s'en trouvaient considérablement améliorées. With the aim of continuing to increase the real part of the relative dielectric permittivity of ceramics, the Applicant has surprisingly demonstrated, by appropriately selecting the operating conditions of their manufacturing process, the dielectric performances of the materials obtained. considerably improved.
Ainsi la présente invention concerne un procédé de préparation de céramiques à base de titanate de baryum dopé au lanthane comprenant les étapes de : (a) frittage flash de poudres de titanate de baryum dopé au lanthane, à une température comprise entre 950 C et 1050 C, pendant une durée comprise entre 1 et 10 mn, sous une pression d'au moins 50 MPa, (b) traitement thermique du matériau ainsi obtenu à une température comprise entre 800 C et 900 C pendant une durée comprise entre 2 et 24 heures, sous atmosphère d'air, ou sous atmosphère oxydante. Thus, the present invention relates to a process for the preparation of ceramics based on lanthanum doped titanate comprising the steps of: (a) flash sintering of lanthanum-doped barium titanate powders at a temperature of between 950.degree. C. and 1050.degree. for a period of between 1 and 10 min, under a pressure of at least 50 MPa, (b) heat treatment of the material thus obtained at a temperature between 800 ° C. and 900 ° C. for a period of between 2 and 24 hours, in an atmosphere of air, or in an oxidizing atmosphere.
Dans un aspect avantageux du procédé selon l'invention, l'étape (a) est effectuée à une température de 1050 C pendant 3 minutes sous un courant de 370 A. Cette étape est conduite sous vide primaire ou sous atmosphère neutre, par exemple sous argon ou sous azote. Préférentiellement elle est réalisée sous vide primaire. In an advantageous aspect of the process according to the invention, step (a) is carried out at a temperature of 10 ° C. for 3 minutes under a current of 370 A. This step is carried out under a primary vacuum or under a neutral atmosphere, for example under argon or under nitrogen. Preferably it is carried out under a primary vacuum.
Selon un autre aspect avantageux du procédé de la présente invention, la température de frittage est obtenue à l'aide d'une rampe de température de 50 C par minute, à partir de la température ambiante, c'est-à-dire à partir d'une température de l'ordre de 25 C. According to another advantageous aspect of the process of the present invention, the sintering temperature is obtained using a temperature ramp of 50 C per minute, starting from the ambient temperature, that is to say from a temperature of the order of 25 C.
La seconde étape du procédé selon l'invention est nécessaire afin d'enlever des traces de carbone provenant de la contamination de la matrice et pour réajuster la teneur en oxygène de l'échantillon. Des conditions spécifiques de traitement thermique telles que mentionnées ci-dessus permettent non seulement d'atteindre cet objectif, mais également d'influencer les propriétés électriques des céramiques obtenues et en particulier de leur conférer un caractère isolant. Cette étape est réalisée sous atmosphère oxydante, ou alternativement sous atmosphère d'air. La diffusion de l'oxygène durant cette étape semble conduire à une répartition hétérogène, mais surtout permet d'obtenir des valeurs de la partie réelle de la permittivité diélectrique relative jamais observées jusqu'alors. Les céramiques susceptibles d'être obtenues par le procédé ci-dessus présentent une partie réelle de la permittivité diélectrique relative supérieure à 100 000. Cette valeur mesurée à 1 kHz est en particulier de 270 000 sur une large gamme de température, The second step of the process according to the invention is necessary in order to remove traces of carbon originating from the contamination of the matrix and to readjust the oxygen content of the sample. Specific heat treatment conditions as mentioned above not only make it possible to achieve this objective, but also to influence the electrical properties of the ceramics obtained and in particular to give them an insulating nature. This step is carried out under an oxidizing atmosphere, or alternatively under an atmosphere of air. The diffusion of oxygen during this step seems to lead to a heterogeneous distribution, but especially allows to obtain values of the real part of the relative dielectric permittivity never observed until then. The ceramics that can be obtained by the above process have a real part of the relative dielectric permittivity greater than 100,000. This value measured at 1 kHz is in particular 270,000 over a wide temperature range.
Dans un aspect préféré du procédé tel que mentionné ci-dessus, l'étape (b) s'effectue à une température de 850 C, pendant 2 heures sous atmosphère d'air. Le matériau de départ utilisé pour la mise en oeuvre du procédé selon l'invention est le titanate de baryum (BaTiO3) dopé au lanthane. Ce matériau peut être représenté par la formule : LaXBa(l _X)Ti(l _x/4)03 15 dans laquelle 0<x<0,14. Dans un aspect préféré de l'invention, x est compris entre 0,04 et 0,06, et de façon particulière, la valeur de x est fixée à 0,048. In a preferred aspect of the process as mentioned above, step (b) is carried out at a temperature of 850 ° C for 2 hours in an air atmosphere. The starting material used for carrying out the process according to the invention is lanthanum doped barium titanate (BaTiO 3). This material may be represented by the formula: LaXBa (I _X) Ti (I _x / 4) O in which 0 <x <0.14. In a preferred aspect of the invention, x is between 0.04 and 0.06, and in particular, the value of x is set at 0.048.
Ce matériau de départ peut être préparé par des techniques conventionnelles de 20 chimie douce ou par voie solide-solide. Pour la mise en oeuvre de la présente invention, on préférera les méthodes de chimie douce. Parmi elles, sont choisies les méthodes de co-précipitation, ou les méthodes de synthèse hydrothermales. Les méthodes de co-précipitation reposent sur une réaction de double décomposition entre un sel métallique et un oxalate 25 alcalin, ou entre un sel métallique et l'acide oxalique. La synthèse hydrothermale permet d'obtenir directement les poudres d'oxydes cristallisés à l'issu d'un traitement sous pression autogène. Le titanate de baryum peut être synthétisé à partir d'une solution basique de trichlorure de titane, de chlorure de baryum et de chlorure de lanthane. Dans certains cas ; la présence d'un agent complexant est 30 indispensable pour pouvoir dissoudre les deux oxydes simples sur un même domaine de pH et assurer la précipitation de l'oxyde mixte final. Les poudres10 d'oxalates ainsi obtenues sont ensuite calcinées pour conduire aux oxydes correspondants. This starting material can be prepared by conventional soft-chemistry or solid-solid techniques. For the implementation of the present invention, the methods of soft chemistry will be preferred. Among them are chosen co-precipitation methods, or hydrothermal synthesis methods. The co-precipitation methods are based on a double decomposition reaction between a metal salt and an alkaline oxalate, or between a metal salt and oxalic acid. Hydrothermal synthesis makes it possible to obtain crystalline oxide powders directly from an autogenous pressure treatment. Barium titanate can be synthesized from a basic solution of titanium trichloride, barium chloride and lanthanum chloride. In some cases ; the presence of a complexing agent is essential in order to be able to dissolve the two simple oxides on the same pH range and to ensure the precipitation of the final mixed oxide. The oxalate powders thus obtained are then calcined to yield the corresponding oxides.
Dans un aspect avantageux de l'invention on choisira la méthode de co-précipitation de sels métalliques et de l'acide oxalique dans un solvant organique. Plus spécifiquement, les sels précurseurs sont les sels de dichlorure de baryum (BaC12,2H2O) et de trichlorure de titane (TiC13). Le précurseur de lanthane est le trichlorure de lanthane (LaC13, 7H2O). Il est ajouté à la solution de chlorures métalliques. Les poudres d'oxalates sont préparées par coprécipitation de la solution aqueuse de chlorures métalliques par une solution éthanoïque d'acide oxalique. Le temps de mûrissement peut être avantageusement de 5 heures 30 minutes. Une étape ultérieure de calcination conduit aux poudres de titanate de baryum utilisées comme matériau pour la mise en oeuvre du procédé selon l'invention. Cette étape est réalisée par exemple à une température de 850 C. De façon avantageuse, le diamètre des poudres de titanate de baryum utilisées est compris entre 10 nm et 500 nm. In an advantageous aspect of the invention, the method of co-precipitation of metal salts and oxalic acid in an organic solvent will be chosen. More specifically, the precursor salts are the salts of barium dichloride (BaC12.2H2O) and titanium trichloride (TiCl3). The precursor of lanthanum is lanthanum trichloride (LaC13, 7H2O). It is added to the solution of metal chlorides. The oxalate powders are prepared by coprecipitation of the aqueous solution of metal chlorides with an ethanoic solution of oxalic acid. The ripening time may advantageously be 5 hours 30 minutes. A subsequent calcination step leads to barium titanate powders used as a material for carrying out the process according to the invention. This step is carried out for example at a temperature of 850 ° C. Advantageously, the diameter of the barium titanate powders used is between 10 nm and 500 nm.
La présente invention concerne également les céramiques susceptibles d'être obtenues selon le procédé mentionné ci-dessus. Comme indiqué plus haut, les propriétés diélectriques de ces matériaux s'en trouvent améliorées. C'est le cas notamment la partie réelle de la permittivité diélectrique relative qui atteint des valeurs encore jamais observées. L'invention concerne donc des céramiques à base de titanate de baryum dopé au lanthane qui présentent une partie réelle de la permittivité diélectrique relative supérieure à 100 000 mesurée à 1 kHz. Dans un aspect préféré cette valeur mesurée à 1 kHz est de 270 000. The present invention also relates to ceramics that can be obtained according to the method mentioned above. As indicated above, the dielectric properties of these materials are improved. This is the case in particular the real part of the relative dielectric permittivity which reaches values never observed before. The invention thus relates to ceramics based on lanthanum doped barium titanate which have a real part of the relative dielectric permittivity greater than 100 000 measured at 1 kHz. In a preferred aspect, this value measured at 1 kHz is 270,000.
De plus, les facteurs de pertes mesurés, qui caractérisent la dissipation totale d'énergie, sont relativement faibles, ce qui présente un avantage supplémentaire. In addition, the measured loss factors, which characterize the total energy dissipation, are relatively small, which has an additional advantage.
Ils sont notamment compris entre 0,1 et 0,2 à une température variant de -100 C à + 150 C pour une fréquence de 1 kHz. They are in particular between 0.1 and 0.2 at a temperature ranging from -100 ° C. to + 150 ° C. for a frequency of 1 kHz.
La mise en oeuvre du procédé selon l'invention permet de contrôler la croissance de la taille des grains de la céramique. L'invention concerne donc aussi des céramiques à base de titanate de baryum dont la taille de grains est inférieure à 100 nm, et préférentiellement inférieure à 150 nm. L'invention concerne également des céramiques à base de titanate de baryum dopé au lanthane caractérisées par l'absence de comportement ferroélectrique dans la gamme de températures entre -100 C et +200 C. The implementation of the method according to the invention makes it possible to control the growth of the grain size of the ceramic. The invention therefore also relates to ceramics based on barium titanate whose grain size is less than 100 nm, and preferably less than 150 nm. The invention also relates to ceramics based on lanthanum-doped barium titanate characterized by the absence of ferroelectric behavior in the temperature range between -100 C and +200 C.
10 Comme mentionné en introduction, les céramiques à base de titanate de baryum sont largement utilisées pour la fabrication de divers composants passifs qu'ils soient électrostatiques ou électro-optiques. En particulier, concernant les composants passifs, elles peuvent servir à l'obtention de condensateurs monocouches ou multicouches. L'utilisation des céramiques selon la présente 15 invention permet d'atteindre en une seule étape des valeurs de capacités volumiques au moins identiques, voire supérieures, à celles de condensateurs multicouches qui nécessitent un grand nombre d'étapes technologiques, notamment le coulage en bande ou les métallisations internes. As mentioned in the introduction, ceramics based on barium titanate are widely used for the manufacture of various passive components whether electrostatic or electro-optical. In particular, concerning the passive components, they can be used to obtain monolayer or multilayer capacitors. The use of the ceramics according to the present invention makes it possible to achieve, in a single step, volumetric capacitance values at least identical to, or even greater than, those of multilayer capacitors which require a large number of technological steps, in particular band casting. or internal metallizations.
20 L'invention concerne donc également des condensateurs caractérisés en ce qu'ils contiennent les céramiques à base de titanate de baryum dopé au lanthane selon l'invention. Dans un premier temps des condensateurs monocouches ont été obtenus notamment par métallisation des céramiques ainsi obtenues que ce soit par sérigraphie d'électrodes d'argent, par pulvérisation cathodique d'un métal, ou par 25 toute autre méthode permettant la réalisation de contacts électriques. Ils présentent de fortes capacités volumiques, égales voire supérieures à celles mesurées dans le cas de condensateurs commerciaux. En particulier la valeur de la capacité des condensateurs selon l'invention est d'au moins 40 nF à 1 kHz et à la température ambiante, c'est-à-dire de 25 C pour une épaisseur de 1,5 mm et une surface de 0,2 30 cm2. Plus particulièrement, une capacité volumique de 300 nF/cm3 est obtenue5 pour une épaisseur de 1,5 mm et présente une tenue en tension au moins de l'ordre de 1 kV voire supérieure. The invention therefore also relates to capacitors characterized in that they contain ceramics based on lanthanum doped barium titanate according to the invention. At first monolayer capacitors were obtained in particular by metallization of the ceramics thus obtained, whether by screen printing of silver electrodes, by cathodic sputtering of a metal, or by any other method making it possible to produce electrical contacts. They have high volume capacities equal to or even greater than those measured in the case of commercial capacitors. In particular the capacitance value of the capacitors according to the invention is at least 40 nF at 1 kHz and at ambient temperature, that is to say 25 C for a thickness of 1.5 mm and a surface 0.2 cm 2. More particularly, a volume capacity of 300 nF / cm 3 is obtained for a thickness of 1.5 mm and has a tensile strength at least of the order of 1 kV or more.
L'invention concerne aussi l'utilisation des céramiques telles que décrites précédemment pour la fabrication de composants passifs intégrés, notamment des condensateurs monocouches ou multicouches The invention also relates to the use of ceramics as described above for the manufacture of integrated passive components, in particular monolayer or multilayer capacitors.
Description des figures : Figure lA : Micrographie MEB-FEG d'une poudre de composition Ba0,952Lao,04BTio,98803 selon l'invention. DESCRIPTION OF THE FIGURES FIG. 1A: MEB-FEG micrograph of a powder of composition Ba0,952Lao, 04BTio, 98803 according to the invention.
Figure 1B : Micrographies MEB-FEG de la surface de céramiques obtenues selon l'invention. Figure 2A : Mesure de la partie réelle de la permittivité diélectrique relative sur une plage de températures comprises entre -100 C et 150 C pour différentes fréquences. FIG. 1B: SEM-FEG micrographs of the surface of ceramics obtained according to the invention. Figure 2A: Measurement of the real part of the relative dielectric permittivity over a range of temperatures between -100 C and 150 C for different frequencies.
20 Figure 2B : Mesure de facteurs de pertes en fonction de la température pour différentes fréquences. Figure 2B: Measurement of loss factors as a function of temperature for different frequencies.
Figure 3 : Illustration de la reproductibilité de la méthode selon l'invention par la mesure de la partie réelle de la permittivité diélectrique 25 relative pour deux échantillons A et B réalisés dans les mêmes conditions. Figure 3: Illustration of the reproducibility of the method according to the invention by measuring the real part of the relative dielectric permittivity for two samples A and B made under the same conditions.
Les exemples qui suivent servent à illustrer l'invention, mais ne la limitent en aucune façon. 30 Exemple 1 : Préparation de poudres de titanate de baryum dopé au lanthane. The examples which follow serve to illustrate the invention, but do not limit it in any way. Example 1: Preparation of lanthanum doped barium titanate powders
Les sels métalliques précurseurs de métaux utilisés sont : ^ Chlorure de baryum à 2 molécules d'eau (BaCl2, 2H2O) RP NORMAPUR pour analyse (PROLABO) : M=248,28 g/mol, pureté 99,0 %. ^ Chlorure de titane (III) à 15 % en solution aqueuse RP NORMAPUR pour analyse (PROLABO) : M=154,26 g/mol, d=1,2. ^ Chlorure de lanthane à 7 molécules d'eau RP NORMAPUR pour analyse (PROLABO) : M= 371,37g/mol. The metal precursor metal salts used are: 2-water barium chloride (BaCl 2, 2H 2 O) NORMAPUR RP for analysis (PROLABO): M = 248.28 g / mol, purity 99.0%. Titanium (III) chloride 15% in aqueous solution RP NORMAPUR for analysis (PROLABO): M = 154.26 g / mol, d = 1.2. ^ Lanthanum chloride with 7 NORMAPUR RP water molecules for analysis (PROLABO): M = 371.37g / mol.
Le chlorure de lanthane (en proportion souhaitée) est ajouté à une solution de chlorure de baryum (0,125 mol) et de chlorure de titane (0, 125 mol). Le mélange est dilué à l'eau distillée jusqu'à 800 ml pour constituer la solution 1. The lanthanum chloride (in desired proportion) is added to a solution of barium chloride (0.125 mol) and titanium chloride (0.125 mol). The mixture is diluted with distilled water to 800 ml to form solution 1.
L'acide oxalique (47,53 g) est dissout dans 5 1 d'éthanol pour constituer la solution 2. Les deux solutions sont mélangées sous un flux d'air pendant 5 heures 30 minutes pour conduire à la coprécipitation des oxalates mixtes. Après centrifugation, filtration, lavage à l'éthanol, et séchage à 100 C durant une nuit, les poudres ainsi obtenues sont broyées et calcinées à une température de 850 C pour conduire au titanate de baryum dopé au lanthane de formule : Bao,952Lao,o4sTio,988O3. The oxalic acid (47.53 g) is dissolved in 5 l of ethanol to form the solution 2. The two solutions are mixed under a stream of air for 5 hours 30 minutes to lead to the coprecipitation of the mixed oxalates. After centrifugation, filtration, washing with ethanol, and drying at 100 ° C. overnight, the powders thus obtained are ground and calcined at a temperature of 850 ° C. to yield lanthanum doped barium titanate of formula: BaO, 952Lao, o4sTio, 988O3.
Les échantillons obtenus sont observés à l'aide d'un microscope électronique à balayage à effet de champ (JEOL 6700 F). La morphologie des poudres est visible sur la figure 1A. The samples obtained are observed using a field-effect scanning electron microscope (JEOL 6700 F). The morphology of the powders is visible in FIG. 1A.
Exemple 2 : Préparation de céramiques Example 2: Preparation of ceramics
L'étape de frittage flash est réalisée à l'aide d'un appareil SPS (Spark Plasma Sintering) modèle SPS2080 de la société SUMIMOTO (Japon). The flash sintering step is carried out using a SPS (Spark Plasma Sintering) apparatus model SPS2080 from SUMIMOTO (Japan).
La poudre de titanate de baryum dopé au lanthane selon l'exemple 1 (0,9 g) est placée dans une matrice en graphite de diamètre égal à 8 mm et un courant électrique de 370 A est appliqué sous une pression de 50 MPa. L'échantillon est ainsi chauffé jusqu'à 1050 C avec une vitesse de chauffage de 50 C/mn. Après 3 minutes de palier à cette température, le courant électrique est coupé, ainsi que la pression sur l'échantillon. Au bout d'une minute supplémentaire, la température est revenue à 600 C. Les céramiques ainsi obtenues sont ensuite soumises à un traitement thermique à 850 C pendant 2 heures sous atmosphère d'air. The lanthanum doped barium titanate powder according to Example 1 (0.9 g) is placed in a graphite matrix with a diameter of 8 mm and an electric current of 370 A is applied under a pressure of 50 MPa. The sample is thus heated up to 1050 C with a heating rate of 50 C / min. After 3 minutes of bearing at this temperature, the electric current is cut off, as is the pressure on the sample. After another minute, the temperature is returned to 600 C. The ceramics thus obtained are then subjected to heat treatment at 850 C for 2 hours in an air atmosphere.
La reproductibilité du procédé de l'invention a été vérifiée par la réalisation de deux échantillons à partir de la même poudre, et suivant des conditions opératoires identiques. ^ Mesure de la densité apparente des céramiques La pesée hydrostatique dans l'eau est utilisée pour déterminer la densité apparente des céramiques. La balance électronique utilisée est de marque Kern ARJ220-4 M. Elle permet la mesure de masse comprise entre 0 et 220 g (précision de 10-4 g). Les densités sont données par la formule : d= mai. / (mairù meau), dans laquelle mai,. est la masse dans l'air et menu est la masse dans l'eau. Les densifications sont exprimées en % de la densité théorique. The reproducibility of the process of the invention was verified by producing two samples from the same powder, and under identical operating conditions. ^ Measurement of the apparent density of ceramics Hydrostatic weighing in water is used to determine the apparent density of ceramics. The electronic scale used is branded Kern ARJ220-4 M. It allows the measurement of mass between 0 and 220 g (precision of 10-4 g). The densities are given by the formula: d = May. / (mairù meau), in which may ,. is the mass in the air and menu is the mass in the water. The densifications are expressed in% of the theoretical density.
^ Résultats : La densification des deux céramiques obtenues est de : Echantillon 1 : 96,1 % Echantillon 2 : 97,2 Results: The densification of the two ceramics obtained is: Sample 1: 96.1% Sample 2: 97.2
La morphologie des échantillons est observée à l'aide d'un microscope électronique à balayage à effet de champ (JEOL 6700 F) La surface de chaque échantillon est représentée sur la figure 1B. The morphology of the samples is observed using a field-effect scanning electron microscope (JEOL 6700 F). The surface of each sample is shown in FIG. 1B.
Dans chaque cas la taille des particules est inférieure à 150 rira. In each case the particle size is less than 150 rira.
^ Détermination de la partie réelle de la permittivité diélectrique relative s'r Pour déterminer la partie réelle de la permittivité diélectrique relative et le facteur de pertes, on utilise généralement un modèle simple dans lequel le diélectrique est assimilé à un condensateur imparfait représenté par une capacité parfaite de dimension finie, de surface S et d'épaisseur e et par une résistance. Ceci conduit à : Determination of the real part of the relative dielectric permittivity To determine the real part of the relative dielectric permittivity and the loss factor, a simple model is generally used in which the dielectric is assimilated to an imperfect capacitor represented by a capacitance. perfect finite size, S surface and thickness e and a resistor. This leads to:
C.e sr= so.S et à tgô = 1 sr R.Cw sr où so est la permittivité du vide, S'r la partie réelle de la permittivité diélectrique relative, E"r la partie imaginaire de la permittivité diélectrique relative, R est la valeur de la résistance, C la valeur de la capacité et, co est la pulsation déterminée suivant la formule co = 2nf où f est la fréquence du signal utilisé. La permittivité complexe relative s*r est donnée par la formule s*, = s'r js"r La grandeur tgô correspond aux pertes diélectriques (cette grandeur est encore appelée facteur de pertes ). Elle caractérise la dissipation totale d'énergie du diélectrique quand un champ électrique lui est appliqué. D'un point de vue expérimental, ces grandeurs sont déterminées par la mesure de la capacité C et la résistance R. La possibilité d'effectuer cette mesure à des fréquences et des températures variables permet d'étendre l'analyse et de mieux comprendre les relations propriétés électriques /structures. This sr = so.S and tgô = 1 sr R.Cw sr where so is the permittivity of the vacuum, S'r the real part of the relative dielectric permittivity, E "r the imaginary part of the relative dielectric permittivity, R is the value of the resistance, C the value of the capacitance and, co is the pulsation determined according to the formula co = 2nf where f is the frequency of the signal used The relative complex permittivity s * r is given by the formula s *, = The size tg6 corresponds to the dielectric losses (this quantity is still called the loss factor). It characterizes the total energy dissipation of the dielectric when an electric field is applied to it. From an experimental point of view, these quantities are determined by the measurement of the capacitance C and the resistance R. The possibility of carrying out this measurement at variable frequencies and temperatures makes it possible to extend the analysis and to better understand the relations electrical properties / structures.
Les mesures sont réalisées à l'aide des appareils suivants : 1. Système I : Un pont de mesure d'impédance de type HP 4284A dont la gamme de fréquence s'étend de 20Hz à 1MHz. Measurements are made using the following devices: 1. System I: An impedance measuring bridge type HP 4284A whose frequency range extends from 20Hz to 1MHz.
Un analyseur de gain et de phase HP 4194A dont la gamme de fréquence s'étend de 40Hz à 110MHz Une enceinte régulée en température dans la gamme de -75 C à 160 C, Un ordinateur PC pour automatiser le processus de mesure 10 2. Système II : Un T. A. INSTRUMENT DEA 2970 dans la gamme de fréquences de 0.1Hz à 100kHz, Une enceinte thermostatée qui peut régler la température de -200 C à 160 C, Un ordinateur PC pour automatiser le processus de mesure 15 Résultats : Les résultats sont regroupés sur la figure 2A pour les mesures de la partie réelle de la permittivité diélectrique relative et sur la figure 2B pour les mesures de du facteur de pertes. La reproductivité du procédé de fabrication des céramiques selon l'invention 20 est illustrée sur la figure 3. HP 4194A Gain and Phase Analyzer with Frequency Range from 40Hz to 110MHz Temperature Controlled Speaker in the Range of -75 C to 160 C, A PC to Automate the Measuring Process 10 2. System II: A TA INSTRUMENT DEA 2970 in the frequency range from 0.1Hz to 100kHz, A thermostatically controlled chamber that can adjust the temperature from -200 C to 160 C, A PC computer to automate the process of measurement 15 Results: The results are grouped in FIG. 2A for measurements of the real part of the relative dielectric permittivity and in FIG. 2B for measurements of the loss factor. The reproductivity of the ceramics manufacturing process according to the invention is illustrated in FIG.
Les valeurs de la partie réelle de la permittivité diélectrique relative mesurées sont très élevées pour des fréquences comprises entre 1Hz et 10kHz, et sur toute la plage de température. De plus, ces valeurs sont quasiment constantes pour les trois premières 25 fréquences étudiées. The values of the real part of the relative dielectric permittivity measured are very high for frequencies between 1Hz and 10kHz, and over the entire temperature range. In addition, these values are almost constant for the first three frequencies studied.
La variation des pertes observées (tgô) traduit un minimum de perte d'énergie sur la plage de température et aux fréquences étudiées. The variation in observed losses (tgô) reflects a minimum of energy loss over the temperature range and the frequencies studied.
Claims (15)
Priority Applications (5)
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| FR0603414A FR2900148B1 (en) | 2006-04-19 | 2006-04-19 | CERAMICS BASED ON LANTHAN DOPED BARIUM TITANATE, NOVEL PREPARATION METHOD AND USES. |
| EP07728266.3A EP2013155B1 (en) | 2006-04-19 | 2007-04-18 | Ceramics based on lanthanum-doped barium titanate, method of preparation and uses |
| JP2009505884A JP5325095B2 (en) | 2006-04-19 | 2007-04-18 | Ceramics based on lanthanum-doped barium titanate, process for its production and use |
| US12/226,420 US7939007B2 (en) | 2006-04-19 | 2007-04-18 | Ceramics based on lanthanum-doped barium titanate, method of preparation and uses |
| PCT/EP2007/053804 WO2007118897A1 (en) | 2006-04-19 | 2007-04-18 | Ceramics based on lanthanum-doped barium titanate, method of preparation and uses |
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| FR0603414A FR2900148B1 (en) | 2006-04-19 | 2006-04-19 | CERAMICS BASED ON LANTHAN DOPED BARIUM TITANATE, NOVEL PREPARATION METHOD AND USES. |
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| US8263515B2 (en) | 2009-08-29 | 2012-09-11 | Fatih Dogan | Nanostructured dielectric materials for high energy density multi layer ceramic capacitors |
| US8181134B2 (en) | 2009-10-16 | 2012-05-15 | International Business Machines Corporation | Techniques for performing conditional sequential equivalence checking of an integrated circuit logic design |
| CN102093047B (en) * | 2011-01-04 | 2013-01-23 | 天津师范大学 | Sintering method for increasing dielectric constant of barium titanate |
| JP2012253321A (en) * | 2011-05-09 | 2012-12-20 | Tohoku Univ | Electricity storage material and electronic component using the same |
| KR101575244B1 (en) * | 2013-12-09 | 2015-12-08 | 현대자동차 주식회사 | Dielectric material for temperature compensation and method of preparing the same |
| KR101905143B1 (en) * | 2017-05-11 | 2018-10-08 | 한국과학기술원 | Nonferroelectric dielectric materials and method thereof |
| US11230501B1 (en) | 2018-03-29 | 2022-01-25 | United States Of America As Represented By The Administrator Of Nasa | Method of fabricating high-permittivity dielectric material |
| CN112374536A (en) * | 2020-10-19 | 2021-02-19 | 中国工程物理研究院材料研究所 | Rapid preparation of spinel type Li at low temperature4Ti5O12Method for preparing lithium titanate material |
| CN112500155B (en) * | 2020-11-09 | 2022-06-14 | 中国科学院宁波材料技术与工程研究所 | Preparation method of lanthanum-doped barium titanate target |
| CN115490511B (en) * | 2022-09-16 | 2023-06-06 | 大连达利凯普科技股份公司 | Low-temperature cofiring material with near-zero temperature coefficient and preparation method thereof |
| CN117059399B (en) * | 2023-10-11 | 2024-01-26 | 北京航空航天大学宁波创新研究院 | Preparation method of dielectric capacitor based on roll-to-roll and dielectric capacitor |
| CN117735979B (en) * | 2023-10-20 | 2024-06-14 | 中国矿业大学 | Ceramic dielectric material with ultra-wide temperature stability and high temperature low loss and rapid sintering preparation method thereof |
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| JPH06302214A (en) * | 1993-04-19 | 1994-10-28 | Kyocera Corp | Dielectric porcelain |
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| FINLAY D. MORRISON ET AL.: "Novel Doping Mechanism for Very-High-Permittivity Barium Titanate Ceramics", J. AM. CERAM. SOC., vol. 81, no. 7, 1998, pages 1957 - 1960, XP002405395 * |
| TOMONARI TAKEUCHI ET AL.: "Preparation of Dense BaTiO3 Ceramics with Submicrometer Grains by Spark Plasma Sintering", J. AM. CERAM. SOC., vol. 82, no. 4, 1999, pages 939 - 943, XP002405396 * |
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| US7939007B2 (en) | 2011-05-10 |
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| EP2013155B1 (en) | 2013-08-21 |
| US20100027191A1 (en) | 2010-02-04 |
| FR2900148B1 (en) | 2008-07-11 |
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| WO2007118897A1 (en) | 2007-10-25 |
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